Search results for "Function"

DFT modelling of oxygen adsorption on the Ag-doped LaMnO3 (001) surface

2019

This study was partly financed by the State Education Development Agency of the Republic of Latvia via the Latvian State Scholarship (A.A.) and Latvia-Ukraine Project (Grant LV-UA/2018/2 to E.K.). The work of T.I. is performed under the state assignment of IGM SB RAS. Also, this research was partly supported by the Ministry of Education and Science of the Republic of Kazakhstan in the framework of the scientific and technology Program BR05236795 ‘‘Development of Hydrogen Energy Technologies in the Republic of Kazakhstan’’. The authors thank M. Sokolov for technical assistance and valuable suggestions.

From Mono- to Poly-Substituted Frameworks: A Way of Tuning the Acidic Character of C-c-H in o-Carborane Derivatives

2009

[EN] The incorporation of iodine atoms onto the boron vertices of the o-carborane framework causes, according to spectroscopic data, a uniform increase in the acidic character of the C-c-H (C-c= cluster carbon) vertices, whereas the incorporation of methyl groups onto the boron vertices of the o-carborane framework reduces their acidity. Methyl groups when attached to boron are electron-withdrawing in boron clusters, whereas iodine atoms bonded to boron act as electron donors. This has been proven on B-methyl and B-iodinated o-carboranes with NMR spectroscopy measurements and DFT calculations of natural bond orbital (NBO) charges. which show a Cumulative buildup of positive cluster only tot…

Adenine nucleotide metabolism during anoxia and postanoxic recovery in insects

1996

Severe hypoxia (anoxia), if maintained for more than a few minutes, causes irreversible damage in humans and other mammals. Why mammals are so vulnerable to anoxia is not fully understood. It is therefore of interest to study animals that are more tolerant of anoxia in order to identify physiological and metabolic properties that are correlated with a high tolerance of anoxia. Insects have high metabolic rates and their energy metabolism is dependent on aerobic ATP production. In insects, as in mammals, anoxia causes a rapid breakdown of physiological function, resulting in a state similar to rigor mortis. This is accompanied by a precipitous decrease in metabolic rate. In contrast to mamma…

Atomistic Insights into Nitrogen-Cycle Electrochemistry: A Combined DFT and Kinetic Monte Carlo Analysis of NO Electrochemical Reduction on Pt(100)

2017

Electrocatalytic denitrification is a promising technology for the removal of NOx species in groundwater. However, a lack of understanding of the molecular pathways that control the overpotential and product distribution have limited the development of practical electrocatalysts, and additional atomic-level insights are needed to advance this field. Adsorbed NO has been identified as a key intermediate in the NOx electroreduction network, and the elementary steps by which it decomposes to NH4+, N2, NH3OH+, or N2O remain a subject of debate. Herein, we report a combined density functional theory (DFT) and kinetic Monte Carlo (kMC) study of this reaction on Pt(100), a catalytic surface that i…

1988

Negatively charged lipid molecules were converted into polymerizable lipids by introduction of polymerizable mono- or bifunctional counterions. As an attempt to mimic the cytoskeleton of biomembranes, unsymmetrical polymeric vesicles were prepared, where the polyelectrolyte is attached either only to the inner or to the outer bilayer surfaces. Polymerizable cations were introduced to the outer surface of preformed small unilamellar vesicles via ion-exchange. The outer counterions of vesicles bearing polymerizable counterions at both sides of the membrane were replaced by Na+. Polymerization of these systems leads to unsymmetrical vesicles. The introduction, separation and polymerization of …

Bifunctional Acid-Base Catalysis

2011

Acid-base catalysis with bifunctional catalysts is a very prominent catalytic strategy in both small-molecule organocatalysts as well as enzyme catalysis. In both worlds, small-molecule catalysts and enzymatic catalysis, a variety of different general acids or hydrogen bond donors are used. In this chapter, important parallels between small molecule catalysts and enzymes are discussed, and a comparison is also made to the emerging field of frustrated Lewis pair catalysis.

Study of the role of sulfur functionalities in humic acids for uranium(VI) complexation

2009

Humic substances influence the speciation and migration behavior of toxic and radiotoxic metal ions, such as actinides, in the environment. Depending on their origin, humic substances contain different amounts of sulfur ranging from 0.1 to 3.6% and 0.5 to 1.43% in soil and aquatic humic substances, respectively [1]. Reduced, intermediately oxidized and highly oxidized sulfur functionalities occur in humic substances [1]. Although sulfur functionalities occur in small concentrations, they can play an important role in the complexation of selected metal ions. Knowledge about the impact of sulfur functionalities on the metal ion complexation by humic substances and their significance compared …

From Single Molecules to Nanoscopically Structured Materials: Self-Assembly of Metal Chalcogenide/Metal Oxide Nanostructures Based on the Degree of P…

2011

A chemically specific and facile method for the immobilization of metal oxide nanoparticles onto the surface of IF-MoS2 nested fullerenes is reported. The modification strategy is based on the chalcophilic affinity of transition metals such as Fe2+/Fe3+, Fe3+, or Zn2+ as described by the Pearson HSAB concept. The binding capabilities of the 3d metals are dictated by their Pearson hardness. Pearson hard cations such as Fe3+ (Fe2O3) do not bind to the chalcogenide surfaces; borderline metals such as Fe2+ (Fe3O4) or Zn2+ (ZnO) bind reversibly. Pearson-soft metals like Au bind irreversibly. The immobilization of metal oxide nanoparticle colloids was monitored by transmission electron microscopy…

Organocatalysts Fold to Generate an Active Site Pocket for the Mannich Reaction

2017

Catalysts containing urea, thiourea and tertiary amine groups fold into a three-dimensional organized structure in solution both in the absence as well as in the presence of substrates or substrate analogues, as indicated by solution NMR and computational studies. These foldamer catalysts promote Mannich reactions with both aliphatic and aromatic imines and malonate esters. Hammett plot and secondary kinetic isotope effects provide evidence for the C-C bond forming event as the turnoverlimiting step of the Mannich reaction. Computational studies suggest two viable pathways for the C-C bond formation step, differing in the activation modes of the malonate and imine substrates. The results sh…

L'ÉMOTION ET LA RAISON : L'EFFET MODÉRATEUR DU GENRE SUR LE COMPORTEMENT D'ACHAT EN LIGNE

2018

RESUMEN: A pesar de la evidencia existente en torno a las diferencias entre mujeres y hombres en los procesos de toma de decisiones, así como en la adopción de la tecnología, la investigación llevada a cabo hasta la fecha no ha sido concluyente. El objetivo de este trabajo es estudiar las intenciones comportamentales de los consumidores según su género en los intercambios comerciales B2c. En este sentido, se propone identificar cómo el valor funcional -representando el raciocinio del consumidor-, el valor simbólico -representando la motivación emocional- y la confianza actúan como antecedentes de la intención de compra en el canal online. A partir de los resultados derivados de una investig…